EP4305035A1 - Verfahren zur herstellung von amidinen - Google Patents

Verfahren zur herstellung von amidinen

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Publication number
EP4305035A1
EP4305035A1 EP22707899.5A EP22707899A EP4305035A1 EP 4305035 A1 EP4305035 A1 EP 4305035A1 EP 22707899 A EP22707899 A EP 22707899A EP 4305035 A1 EP4305035 A1 EP 4305035A1
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EP
European Patent Office
Prior art keywords
catalyst
process according
dehydration
carried out
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22707899.5A
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English (en)
French (fr)
Inventor
Nicola Vecchini
Federico MONDINI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Versalis SpA
Original Assignee
Versalis SpA
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Filing date
Publication date
Application filed by Versalis SpA filed Critical Versalis SpA
Publication of EP4305035A1 publication Critical patent/EP4305035A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina

Definitions

  • the present invention relates to a process for preparing amidines.
  • the present invention relates to a method for producing amidines such as, for example, l,8-Diazabicyclo[5.4.0]undec-7-ene (from this point of the document onwards indicated in the abbreviated form DBU), or derivatives thereof starting from lactams, such as e-caprolactam and a,b unsaturated nitriles, such as for example acrylonitrile.
  • amidines such as, for example, l,8-Diazabicyclo[5.4.0]undec-7-ene (from this point of the document onwards indicated in the abbreviated form DBU), or derivatives thereof starting from lactams, such as e-caprolactam and a,b unsaturated nitriles, such as for example acrylonitrile.
  • DBU DBU is a versatile molecule that lends itself to numerous applications; in fact the chemical reactions in which it can take part are varied.
  • DBU is used in the catalysis of polyurethanes, in the pharmaceutical industry, in ionic liquids and in general in organic syntheses.
  • DBU 1,8- Diazabicyclo [5.4.0] undec-7-ene
  • the industrial production of DBU mainly occurs through three reaction steps.
  • e-caprolactam is reacted with acrylonitrile to obtain N-(2-cyanoethyl)-a-caprolactam.
  • N-(2-cyanoethyl)-a- caprolactam is hydrogenated to the corresponding amine in the presence of anhydrous ammonia and Nickel Raney catalyst.
  • the N-(3- a m i n o p o p y 1 ) - e - c a p o 1 a c t a m is dehydrated by acid catalysis obtaining DBU.
  • the industrially most complex step of the synthesis is represented by hydrogenation in the presence of ammonia.
  • the catalyst normally used is Nickel-Raney which in its activated form is pyrophoric.
  • Anhydrous ammonia is also a toxic gas and requires specific precautions and authorizations for its storage, use and transport.
  • the process takes place through the dehydration of amino lactam catalyzed by mineral or sulphonic acids (e.g. p-toluenesulfonic acid) in the presence of a solvent, e.g. Xylene.
  • a solvent e.g. Xylene.
  • the reaction mixture is heated to boiling, the dehydration water that forms is condensed together with the solvent and then separated; the solvent is refluxed into the reaction flask.
  • the patent does not describe the steps preceding dehydration, but refers to the known art.
  • the patent EP0347757 A2 describes a method for the synthesis of cyanoalkyl lactams (first step of the industrial process previously described) through the reaction of a lactam and a, b unsaturated nitrile using the same DBU as basic catalyst; DBU can also be used as a solvent.
  • the document does not mention the other reaction steps (second and third), but merely refers to the catalytic hydrogenation of the cyano alkyl lactam as per known art; in fact in example 2 the hydrogenation in the presence of Ni Raney and ammonia is described.
  • Patent CN101279973 B describes a method for the preparation of 1,8- Diazabicyclo-[5.4.0]-undec-7-ene, starting from e-caprolactam and acrylonitrile, in the presence of tert-butyl or tert-amyl alcohol, as a solvent, and NaOH as a catalyst.
  • the reaction product of this first step is subjected to hydrogenation in the presence of anhydrous ammonia and Ni Raney as catalyst. After the hydrogenation, the mixture is neutralized with sulfuric acid, the solvent is recovered and the reaction product is subjected to dehydration with water removal, as described in the German patent DE1545855.
  • Patent publication CN109796458 A describes a method for the preparation of l,8-Diazabicyclo-[5.4.0]-undec-7-ene, always starting from e-caprolactam and acrylonitrile. This time the document no longer describes the hydrogenation step in the presence of ammonia, but introduces an alternative method using hydroquinone, gaseous anhydrous hydrochloric acid, dichloromethane, sodium perborate and ethylenediaminetetraacetic acid (EDTA). The process is considerably complex with respect to the others described; furthermore, in the face of the elimination of ammonia and Ni-Raney, there is the introduction of a highly aggressive agent (anhydrous HC1) as well as numerous chemical substances.
  • anhydrous HC1 highly aggressive agent
  • the patent EP0913388 B1 describes a method for obtaining amines by hydrogenation of nitriles without using ammonia.
  • the novelty lies in the treatment to which the catalyst is subjected.
  • the catalyst (Cobalt Raney or sponge catalyst) is treated with an aqueous solution of lithium hydroxide or, alternatively, the reaction is carried out in the presence of said solution.
  • the catalyst, through this treatment, must incorporate from 0.1 to 100 mmol of lithium hydroxide per gram.
  • Patent EP0662476 B1 describes the synthesis of bicyclic amidines by reaction of lactones with diamines catalyzed by an acid. The process is carried out in a single reaction step and is followed by purification. The patent also claims the use of these amidines as catalysts for polyurethanes. The synthesis of the DBU is described in example 6 and shows a very low yield of the product, equal to 21%.
  • Patent publication CN1262274 A describes a method for the preparation of l,8-diazabicyclo-[5.4.0]-undec-7-ene always starting from e-caprolactam and acrylonitrile; the peculiarity lies in the use of a mixture of inorganic and organic bases as catalysts in the first reaction step (KOH and DBU).
  • the cyano-derivative obtained is subjected to purification before being subjected to reduction.
  • the second hydrogenation step is carried out in the presence of activated Ni (the catalytic form is not defined) as a catalyst but is not mentioned if in the presence or absence of ammonia.
  • Dehydration is always carried out in acidic conditions, through the use of p-toluenesulphonic acid, and in the absence of solvent; the reaction is continued for a rather long period, i.e. between 35 and 40 hours, obtaining a yield, for this step, of 74.61%.
  • the final cyclization step to give bicyclic amidine is carried out in an acid catalyst, specifically p-toluenesulfonic acid, which is dissolved in the reaction environment and which requires the use of a high-boiling solvent for conducting the reaction.
  • an acid catalyst specifically p-toluenesulfonic acid
  • This translates into a greater complexity of the production plant and of the process - also in relation to the need to separate the catalyst from the reaction mixture - and in a consequent increase in costs.
  • the object of the present invention is therefore the realization of an innovative process for the synthesis of amidines which allows a simplification and a reduction of plant, process and maintenance costs.
  • This purpose is achieved through the use of a suitable heterogeneous catalysis in the dehydration/cyclization reaction, with consequent elimination of both the solvent reflux and the neutralization phase of the mixture (necessary if homogeneous catalysis is used, for example with p-toluenesulfonic acid as catalyst).
  • an aim of the present invention is the preparation of 1,8- Diazabicyclo-[5.4.0] -undec-7-ene (DBU) (usable in the applications previously described) starting from the corresponding N-(amino-alkyl) lactam, through the use of heterogeneous catalysis and consequent elimination of solvent reflux and neutralization.
  • DBU 1,8- Diazabicyclo-[5.4.0] -undec-7-ene
  • the Applicant therefore posed the problem of finding a process for producing amidines starting from N-(amino-alkyl) lactams.
  • the Applicant has now found a method for the preparation of amidines starting from N-(amino-alkyl) lactams, comprising the dehydration/cyclization of the amino compound to obtain the amidine, which can finally be subjected to a final step of separation and purification to obtain the product in the form suitable for industrial use.
  • This method can be carried out in batch or continuously; continuous mode is preferred.
  • N-(amino-alkyl) lactams can be prepared using one of the processes described in the state of the art, such as those previously described, or, more preferably, according to the method described in the co-pending Italian patent application entitled “METHOD FOR PREPARING AMIDINE” of the same Applicant, filed on the same day of this application with the number 102021000005321.
  • Suitable reduction catalysts are commercial or synthetic hydrogenation systems, based on one or more metals of groups 8, 9 and 10 of the periodic table, such as for example Iron, Cobalt, Nickel, or noble metals such as Ruthenium, Rhodium, Palladium, Osmium, Mdium or Platinum. Cobalt, Nickel, Palladium and Platinum are preferred. Cobalt and Nickel are particularly preferred. These catalysts can be used in dispersed, colloidal or supported / bound phase, preferably in supported / bound form on inorganic phase with a high surface area, even more preferably in supported / bound phase on silica, alumina or silica-alumina.
  • the Applicant has found that it is possible to conduct the synthesis of amidines with reactions in series, eliminating the solvent before the cyclization/dehydration phase and carrying out a single final purification step without the process presenting criticalities, or requiring separation steps of the intermediates of the desired product from the other reaction products, to ensure an acceptable final purity of the desired product and a high yield and conversion into the desired product in each of the intermediate steps.
  • This aspect therefore makes it possible to simplify the number of devices to be used and to considerably reduce the complexity of the overall process.
  • the object of the present invention is a process for preparing amidines or derivatives thereof of formula (V) starting from N-(amino-alkyl) lactam having the following formula (IV) wherein:
  • R1 is H or an aliphatic hydrocarbon group, optionally substituted, having from 1 to 5, preferably from 1 to 2 carbon atoms, and is more preferably H;
  • R2 is H or an aliphatic hydrocarbon group, optionally substituted, having from 1 to 5, preferably from 1 to 2 carbon atoms, and is more preferably H;
  • R3 is H or an aliphatic hydrocarbon group, optionally substituted, having from 1 to 5, preferably from 1 to 2 carbon atoms, and is more preferably H;
  • R4 is H or an aliphatic hydrocarbon group, optionally substituted, having from 1 to 5, preferably from 1 to 2 carbon atoms, and is more preferably H;
  • R5 is H or an aliphatic hydrocarbon group, optionally substituted, having from 1 to 5, preferably from 1 to 2 carbon atoms, and is more preferably H; m is an integer from 3 to 7, more preferably 3 to 6, wherein even more preferably, (V) is l,8-Diazabicyclo[5.4.0]undec-7-ene, (DBU), said process comprising the following step:
  • amidine of formula (V) synthesized as described above according to the present invention, can be subjected to subsequent purification with the methods known to those skilled in the art.
  • cyclic amidines as defined in formula (V) are also intended.
  • the term "derivative of amidine” means any compound obtainable from amidine by reaction with a carboxylic acid, epoxy ketone, cloroformates or diesters of carbonic acid.
  • step (A) of the process according to the present invention a controlled catalytic addition reaction is carried out to obtain the compound of formula (III) with high yields starting from a lactam of formula (I), preferably e- caprolactam, and a b unsaturated nitrile of formula (II), preferably acrylonitrile, in the presence of a suitable basic catalyst.
  • a lactam of formula (I) preferably e- caprolactam
  • a b unsaturated nitrile of formula (II) preferably acrylonitrile
  • lactam of formula (IV) is subjected to dehydration to give the corresponding amidine, in the preferred case DBU (l,8-Diazabicyclo[5.4.0]undec-7-ene), as described below.
  • DBU l,8-Diazabicyclo[5.4.0]undec-7-ene
  • the reaction mixture coming from the step of hydrogenation, is preferably subjected to recovery of the solvent by evaporation and subsequently to dehydration.
  • the derivative amino of the lactam of formula (IV) can be reacted in purified form.
  • the dehydration is carried out hot, preferably between 90 and 270 °C, more preferably between 130 and 230 °C, even more preferably between 150 and 200 °C, continuously removing the water produced during the dehydration which operates the cyclization.
  • the catalyst is always needed and can be selected from heterogeneous acid catalysts selected from Lewis acids or Lewis acids with Bronsted acid components, such as aluminum oxide (y-AkCk), silico-aluminas (S1O2-AI2O3), earth acids such as lanthanum oxide and zirconium oxide, or heterogeneous resin- based catalysts, such as sulfonated resins or ion exchange resins. Said catalysts can possibly be supported on inert carriers such as, for example, pumice, graphite or silica. Aluminum oxide (y-AkCk), is preferred.
  • the main product of dehydration is the amidine of interest of formula (V).
  • amidine can be purified through one of the methods already known in the art, for example by distillation obtaining a purity ranging from 95 to 98% by weight.
  • the Applicant has therefore surprisingly identified the possibility of carrying out dehydration in the absence of solvent on a solid acid catalyst without refluxing the solvent, in order to facilitate the removal of water, with further simplification of the process and reduction of costs.
  • a solvent typically selected from those usable in known hydrogenation reactions to give the intermediate of formula (IV), for example a xylene is not excluded.
  • reaction step and the final purification step can be carried out continuously.
  • the Applicant has found a new and original process for the producing amidines from lactams.
  • the reactant stream coming from the hydrogenation phase can be sent to a solvent recovery system.
  • the preferred setup is that based on an evaporator for the recovery of the solvent.
  • the reaction mixture with traces of solvent comes out from the bottom of the evaporator.
  • the vapor deriving from the evaporator is fed to the degasser which contains some perforated plates which serve to facilitate both the separation and the contact of the two phases, the liquid one and the vapor one.
  • the vapor phase that leaves the degasser is partially condensed in a reflux type condenser, which operates at a temperature of 20-250 °C, preferably 40-150 °C, even more preferably at 60-130 °C; optionally, further condensation can be carried out to recover also by-products that may be formed during the preceding reactions.
  • the vapors leaving the reflux condenser are condensed, in another condenser, at a temperature between 2-50 °C, preferably 10-30 °C, more preferably 20 °C.
  • the liquid that collects at the outlet of the last condenser is a mixture of solvent and water.
  • the solvent, after the separation of the water, can be recycled, while the mixture that comes out from the bottom of the evaporator can be sent to the dehydration step.
  • Dehydration takes place continuously in a reactor, called dehydrator, preferably of the tubular type, equipped with a heating system and a condensing system formed by a condenser which condenses most of the water that is produced and which sends the condensates to a phase separator.
  • a reactor preferably of the tubular type, equipped with a heating system and a condensing system formed by a condenser which condenses most of the water that is produced and which sends the condensates to a phase separator.
  • the phase separator any traces of organic are separated and reintroduced into the dehydrator, while the water can be partly recycled to a hydrogenation section which can be arranged upstream and the excess sent for treatment.
  • the mixture is fed continuously laterally into the reactor while the steam exits from the reactor head and the reaction product exits from the bottom.
  • Said reactor can optionally contain, in the upper part, fillings such as e.g. rings, plates, septa, such as to
  • the reaction is carried out in the presence of a heterogeneous acid catalyst, preferably g-alumina, with a WHSV (Weight Hourly Space Velocity, relative to the entire reagent mixture) between 1 and 50 h 1 , preferably between 3 and 10 h 1 .
  • the dehydration is carried out hot, preferably between 90 and 270°C, more preferably between 130 and 230°C, even more preferably between 150 and 200°C.
  • the pressure at which the reaction is carried out is comprised between 0.08 and 5 BarA, preferably between 0.5 and 3 BarA, more preferably between 1 and 2 BarA.
  • a stream formed by the dehydration products, any solvent and unreacted amine, and the by-products coming from the previous steps comes out from the bottom of the reactor; in the case in which the compound of formula (IV) is N-(3- aminopropyl)-e-caprolactam, the main product is typically DBU (1,8- Diazabicyclo [5.4.0] undec-7 -ene) .
  • Said stream of products is then sent to a distillation section for the purification of the compound (V), such as for example the DBU. After distillation, the purity of said compound is typically between 95 and 98%.
  • said compound after distillation, can be subjected to further purifications such as liquid-liquid extractions.
  • further purifications such as liquid-liquid extractions.
  • the gas-mass analysis for the determination of reagents and reaction products is carried out with a GC HP6890 chromatograph, equipped with a split/splitless injector and interfaced with a MS HP 5973 mass spectrometer acting as a detector.
  • the chromatograph has an HP- IMS UI capillary column (100% polydimethylsiloxane, Agilent J&W), fused silica WCOT, 30 m long, 0.25 mm ID, 0.25 pm film thickness.
  • the instrumental parameters are as follows:
  • the analyzes on the samples provided were carried out using the Bruker Avance 400 MHz spectrometer, at a temperature of 300 K, dissolving about 50- 70 mg of sample in deuterated chloroform. Spectra were recorded with the following instrumental parameters:
  • Preparation 2 Reaction between e-caprolactam and acrylonitrile in xylene. The same reaction described in preparation 1 was carried out by replacing iso-propanol with xylene and making it react for 2.25 h at the end of the addition of the acrylonitrile (70 °C). GC-MS analysis revealed a conversion of caprolactam of 98.6%, a selectivity of 98.3% and therefore a yield in the product of 96.9%. The basic crude solution was subjected to hydrogenation as described below in preparations 5 and 6.
  • Activation of the catalyst was carried out by first subjecting it to flushing with nitrogen at atmospheric pressure, after which the reactor was heated up to 150 °C with a temperature ramp of 25-50 °C/h, and, once reached such temperature, there has been proceeded with the supply of hydrogen at a flow rate of 30 ml/min, thus raising the temperature up to 180 °C.
  • Preparation 5 hydrogenation of the crude solution in xylene with Co catalyst The same reaction described in preparation 4 was carried out using the mixture coming from preparation 2 and containing xylene instead of iso-propanol. The sample obtained was subjected to GC-MS analysis. The results are reported in table 2.
  • Preparation 6 hydrogenation of the crude solution in xylene with Ni catalyst The same reaction described in preparation 5 was carried out using the commercial catalyst CTZ2, instead of the catalyst CTZ1 (the activation mode is similar to that already described above). The sample obtained was subjected to GC-MS analysis. The results are reported in table 2.
  • Preparation 7 hydrogenation of the crude solution in THF with Co catalyst The same reaction described in preparation 4 was carried out using the mixture coming from preparation 3 and containing THF instead of iso-propanol. The sample obtained was subjected to GC-MS analysis. The results are reported in table 2.
  • Preparation 8 hydrogenation of the crude solution in THF with Ni catalyst The same reaction described in preparation 7 was carried out using the commercial catalyst CTZ2, instead of the catalyst CTZ1. The sample obtained was subjected to GC-MS analysis. The results are reported in table 2.
  • Example 1 dehydration of the crude solution in xylene
  • the solution coming from preparation 5 (138.3 g) was introduced into a flask (containing a few glass balls), connected to a Dean-Stark apparatus equipped with bubble refrigerant.
  • the flask was heated up to 170 °C; the water that formed from the reaction was separated while the solvent was recovered. After about 4 h there was no more water formation; the flask was then cooled and the contents were subjected to GC-MS analysis.
  • the analysis calculated a conversion of N-(3-aminopropyl)-e-caprolactam equal to 94.7%, a selectivity of 99.5% and therefore a yield in DBU of 94.2%.
  • Example 2 Dehydration of the amine with heterogeneous acid catalyst without solvent
  • the flask was then heated up to 170-180 °C for about 5 h (time at which no more condensate formation was noted); the flask was then cooled and the contents were subjected to GC-MS analysis.
  • the analysis calculated a conversion of N-(3-aminopropyl)-e- caprolactam equal to 93.6%, a selectivity of 83.1% and therefore a yield in DBU of 77.8%.
  • Tables 1, 2 and 3 show the summary data of the previous examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Catalysts (AREA)
EP22707899.5A 2021-03-08 2022-03-03 Verfahren zur herstellung von amidinen Pending EP4305035A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102021000005336A IT202100005336A1 (it) 2021-03-08 2021-03-08 Metodo per la preparazione di amidine.
PCT/IB2022/051866 WO2022189910A1 (en) 2021-03-08 2022-03-03 Method for preparing amidines

Publications (1)

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EP4305035A1 true EP4305035A1 (de) 2024-01-17

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EP22707899.5A Pending EP4305035A1 (de) 2021-03-08 2022-03-03 Verfahren zur herstellung von amidinen

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US (1) US20240166656A1 (de)
EP (1) EP4305035A1 (de)
JP (1) JP2024515434A (de)
KR (1) KR20230154845A (de)
CN (1) CN116997552A (de)
IT (1) IT202100005336A1 (de)
TW (1) TW202244045A (de)
WO (1) WO2022189910A1 (de)

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CN116940556A (zh) * 2021-03-08 2023-10-24 维尔萨利斯股份公司 制备脒的方法

Family Cites Families (12)

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Publication number Priority date Publication date Assignee Title
US4943633A (en) * 1988-06-22 1990-07-24 Air Products And Chemicals, Inc. Catalytic preparation of cyanoalkyl lactams
DE3821036A1 (de) * 1988-06-22 1989-12-28 Kunz Gerhard K Verfahren zum behandeln von ionenaustauschermassen, insbesondere zum regenerieren derselben nach enthaertung und entsalzung waessriger loesungen
CA2134009C (en) 1993-11-11 2005-03-08 Oleg Werbitzky Bicyclic amidines, process for their preparation, and their use as catalyst
US5869653A (en) 1997-10-30 1999-02-09 Air Products And Chemicals, Inc. Hydrogenation of nitriles to produce amines
CN1098852C (zh) 1999-02-03 2003-01-15 山东新华工贸股份有限公司 制备1,8－二氮双环[5,4,0]十一烯的方法
JP2003286257A (ja) 2002-01-24 2003-10-10 Nippon Nyukazai Kk ３−アミノプロピル誘導体の製造法
CN1268627C (zh) * 2003-12-01 2006-08-09 吉林省石油化工设计研究院 1.8－二氮杂双环[5，4，0]十一碳－7－烯的制备方法
CN101279973B (zh) 2008-05-22 2010-06-02 山东新华万博化工有限公司 制备1,8－二氮双环[5,4,0]十一烯的方法
GB0814784D0 (en) 2008-08-13 2008-09-17 Johnson Matthey Plc Chemical process
JP5469173B2 (ja) 2008-10-06 2014-04-09 ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー 金属低配合、アルミナ担持触媒組成物及びアミノ化方法
US11352336B2 (en) * 2017-06-29 2022-06-07 The University Of Western Ontario Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural
CN109796458A (zh) 2019-04-09 2019-05-24 淄博鸿润新材料有限公司 一种1,8-二氮杂双环的合成方法

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IT202100005336A1 (it) 2022-09-08
US20240166656A1 (en) 2024-05-23
TW202244045A (zh) 2022-11-16
WO2022189910A1 (en) 2022-09-15
CN116997552A (zh) 2023-11-03
KR20230154845A (ko) 2023-11-09

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